CN104603061A - Method for preparing nanopowder of carbon-coated lithium metal phosphate - Google Patents
Method for preparing nanopowder of carbon-coated lithium metal phosphate Download PDFInfo
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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
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- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
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- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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Abstract
The present invention relates to a method for preparing a nanopowder of a carbon-coated lithium metal phosphate and a nanopowder of lithium metal phosphate manufactured thereby, the preparation method comprising the steps of: (a) preparing a mixed solution by adding a lithium precursor, an iron precursor, and a phosphorous precursor to a glycol-based solvent; (b) preparing a metal glycolate slurry by injecting the mixed solution into a mixer, and heating and condensing same; (c) forming solids by drying the metal glycolate slurry; and (d) preparing the nanopowder of the carbon-coated lithium metal phosphate by firing the solids.
Description
Technical field
The present invention relates to the preparation method of carbon coating lithium iron phosphate nano powder.
Background technology
Along with to the technological development of mobile equipment and the increase of demand, the demand of the secondary cell as the energy is also just sharply increased.In this secondary cell, energy density and voltage high, have extended cycle life, lithium secondary battery that self-discharge rate is low by commercialization, and widely utilized.
Existing lithium secondary battery uses the cobalt/cobalt oxide (LiCoO containing lithium
2) as the main component of positive active material, but due to the security of the above-mentioned cobalt/cobalt oxide containing lithium low, expensive, thus there is the problem being difficult to produce lithium secondary battery in batches.
Recently, compared with lithium, there is the voltage of 3.5V, 3.6g/cm
3high bulk density, 170mAh/g theoretical capacity, and compared with cobalt, not only high temperature safety is excellent, and cheap iron lithium phosphate (LiFePO
4) compound just attracted attention as the positive active material of lithium secondary battery.Just, because the electroconductibility of iron lithium phosphate compound is relatively low, if when therefore iron lithium phosphate compound being used as positive active material, then there is the problem that battery internal resistance increases, thus in order to improve electroconductibility, be necessary on the surface of the particle of above-mentioned iron lithium phosphate compound with thin mode coating electrically conductive material.
As the preparation method of above-mentioned iron lithium phosphate compound, well-known have solid phase method or the liquid phase method such as hydrothermal synthesis method and overcritical water law, researching and developing the hot method of alcohol (glycothermal) using the non-aqueous solution such as ethylene glycol or Diethylene Glycol as reaction solvent recently.The iron lithium phosphate compound particles prepared with aforesaid method, in order to coating electrically conductive material on the surface of above-mentioned particle, is used in mixed conductivity material in the iron lithium phosphate compound of above-mentioned preparation and carries out the mode of calcining.According to aforesaid way, in calcination process, can coated conductive material on the surface of particle, in the case, there is coated conductive material and cannot be uniformly distributed in problem on the surface of above-mentioned particle.
Summary of the invention
The technical problem solved
In order to solve problem as above, there is provided and carry out after heating concentrates and make slurry to adding mixing solutions that lithium, iron and phosphorus precursor prepare in glycols solvent, drying/calcining is carried out to this, thus prepare lithium iron phosphate nano powder, easily can make the method that the carbon comprising the offspring condensed by multiple primary particle applies lithium iron phosphate nano powder thus, above-mentioned primary particle has the carbon of electroconductibility in the uniformly coating of particle.
The means of technical solution problem
An embodiment for realizing above-mentioned purpose of the present invention provides carbon to apply the preparation method of lithium iron phosphate nano powder, aforesaid method comprises: step (a), in glycols solvent, put into lithium precursor, iron precursor and phosphorus precursor to prepare mixing solutions: step (b), drop into above-mentioned mixing solutions to reactor and carry out heating and concentrate and prepare oxyacetic acid metal paste; Step (c), carries out drying to form solids component to above-mentioned oxyacetic acid metal paste; And step (d), calcining is carried out to prepare carbon coating lithium iron phosphate nano powder to above-mentioned solids component.
Another embodiment of the present invention provides the carbon coating lithium iron phosphate nano powder prepared by the preparation method of above-mentioned carbon coating lithium iron phosphate nano powder, above-mentioned carbon coating lithium iron phosphate nano powder packets is containing the offspring condensed by multiple primary particle, and above-mentioned primary particle has olivine crystal structure; Carbon overlay is formed on the part surface of above-mentioned primary particle or whole surface.
Further, another embodiment of the present invention providing package containing above-mentioned carbon coating lithium iron phosphate nano powder positive active material, comprise the positive electrode for lithium secondary battery of above-mentioned positive active material and comprise the lithium secondary battery of above-mentioned positive pole.
The effect of invention
According to the present invention, as the carbon even application of conductive material on primary particle, thus can prepare with high-level efficiency the lithium iron phosphate nano powder that conductance is improved.
Comprise the carbon coating lithium iron phosphate nano powder prepared according to the present invention excellent in capacity and energy density as the lithium secondary battery of positive active material.
Accompanying drawing explanation
Fig. 1 is electron microscope (SEM) photo that the carbon prepared according to one embodiment of the invention applies the primary particle of lithium iron phosphate nano powder.
Fig. 2 is electron microscope (SEM) photo that the carbon prepared according to one embodiment of the invention applies the offspring of lithium iron phosphate nano powder.
Fig. 3 is the chart of the size-grade distribution representing the carbon coating lithium iron phosphate nano powder second particle prepared according to one embodiment of the invention.
Embodiment
Below, the present invention will be described in more detail.
The invention provides when preparing carbon coating lithium iron phosphate nano powder, use glycols solvent as reaction solvent, carry out heating to the mixing solutions being mixed with lithium, iron and phosphorus precursor to concentrate, and carried out the novel method of dry rear calcining, thus effectively can prepare and be coated with carbon equably on the surface at primary particle (individual particle), and comprise and apply lithium iron phosphate nano powder by the carbon of the offspring of plural above-mentioned primary particle phase mutual coagulation.
For realizing in an embodiment of object of the present invention, carbon is provided to apply the preparation method of lithium iron phosphate nano powder, the preparation method of above-mentioned carbon coating lithium iron phosphate nano powder comprises: step (a), in glycols solvent, put into lithium precursor, iron precursor and phosphorus precursor to prepare mixing solutions: step (b), drop into above-mentioned mixing solutions to reactor and carry out heating and concentrate and prepare oxyacetic acid metal paste; Step (c), carries out drying to form solids component to above-mentioned oxyacetic acid metal paste; And step (d), calcining is carried out to prepare carbon coating lithium iron phosphate nano powder to above-mentioned solids component.
Below, be described in detail by different steps.
(step a) for the preparation process of mixing solutions
First, prepare lithium precursor, iron precursor and phosphorus precursor, these are put into glycols solvent, prepare uniform mixing solutions.
Input above-mentioned lithium precursor can for being selected from by Lithium Acetate dihydrate (CH
3cOOLi2H
2o), lithium hydroxide monohydrate (LiOHH
2o), lithium hydroxide (LiOH), Quilonum Retard (Li
2cO
3), Trilithium phosphate (Li
3pO
4), Trilithium phosphate dodecahydrate (Li
3pO
412H
2and lithium oxalate (Li O)
2c
2o
4) one or more mixture in the group that forms.
Input above-mentioned iron precursor can for being selected from by ironic citrate (FeC
6h
5o
7), ironic citrate hydrate (FeC
6h
5o
7nH
2o), FeSO47H2O (FeSO
47H
2o), Ferrox dihydrate (FeC
2o
42H
2o), ferric acetyl acetonade (Fe (C
5h
7o
2)
3), tertiary iron phosphate dihydrate (FePO
42H
2o) one or more the mixture and in the group that forms of ironic hydroxide (FeO (OH)).
Input phosphorus precursor can for being selected from by ammonium phosphate trihydrate ((NH
4)
3pO
43H
2o), Secondary ammonium phosphate ((NH
4)
2hPO
4), primary ammonium phosphate (NH
4h
2pO
4) and phosphoric acid (H
3pO
4) one or more mixture in the group that forms.
In the present invention, be used as glycol (glycol) kind solvent of non-aqueous solution as reaction solvent.
Above-mentioned glycols solvent means and belongs to by general formula R (OH)
2the solvent of the bivalent alcohol class represented, in one embodiment of this invention, above-mentioned glycols solvent can be selected from by ethylene glycol (ethylene glycol), Diethylene Glycol (diethylene glycol) and 1, in the group that 4-butyleneglycol (Isosorbide-5-Nitrae-butandiol) forms.
On the other hand, when preparing above-mentioned mixing solutions, the output-input ratio of lithium, iron and phosphorus precursor, not by particular restriction, such as, can drop into the mol ratio corresponding with 1.0 ~ 1.2:1:1.0 ~ 1.2.
Further, when the amount of the glycols solvent being used as reaction solvent is set to 100 weight part, the iron precursor of about 0.5 to 10 weight part can be dropped into, and lithium precursor and phosphorus precursor can drop into the above-mentioned mol ratio corresponding with above-mentioned iron precursor phase.
When preparing above-mentioned mixing solutions, can also comprise making lithium, iron and phosphorus precursor to be scattered in equably and carrying out as the mode in the glycols solvent of reaction solvent the step that stirs.
the preparation process (step b) of slurry
Then, in reactor, drop into above-mentioned mixing solutions, and prepare oxyacetic acid metal paste by heating to concentrate.
The reactor used can be at the reactor being generally used for preparing lithium iron phosphate nano powder in the technical field of the invention, and the kind of above-mentioned reactor is not by particular restriction.Such as, can be opening reactor or closed type reactor.
Above-mentioned heating concentration process can comprise using the temperature more than for the boiling point of the glycols solvent of reaction solvent to heat, and carries out the process of high-speed stirring to mixing solutions.
On the other hand, in the heating concentration process of above-mentioned steps (b), for the preparation of the speed of the high-speed stirring of slurry at least at more than 10RPM, be then conducive to the glycollate preparing uniform moiety, such as, be preferably within 10 to 200RPM scope.
On the other hand, the time that above-mentioned heating concentration process carries out can be different according to the factor such as heat, stirring velocity of supply when the kind of used above-mentioned glycols solvent, heating, but can carry out such as 1 to 5 hour.
In one embodiment of this invention, when making spent glycol as above-mentioned glycols solvent, at more than about 197 DEG C of the boiling point as ethylene glycol, such as, at the temperature more than about 200 DEG C, carry out the heating concentration process of 2 ~ 5 hours.
On the other hand, the heating concentration process in above-mentioned steps (b) can carry out to the following pressure condition of 10 bar (bar) at normal pressure (normal atmosphere), and above-mentioned pressure condition does not form specific question.
If through above-mentioned heating concentration process, just make oxyacetic acid metal paste.
drying step (step c)
Drying is carried out to the above-mentioned oxyacetic acid metal paste made, thus obtains solids component.
In above-mentioned steps, drying means by particular restriction, such as, in convection oven, can not carry out drying with 100 ~ 180 DEG C of temperature range conditions.
When above-mentioned drying temperature is less than 100 DEG C, the glycols solvent used cannot carry out abundant drying, when drying temperature is greater than 180 DEG C, used glycols solvent content can be made to be thermal decomposited, thus uniform carbon overlay cannot be formed on particle.
calcining step (steps d)
Calcined by the solids component carrying out drying to obtain to above-mentioned oxyacetic acid metal paste, the lithium iron phosphate nano powder of carbon coating can be prepared.
In one embodiment of this invention, above-mentioned calcining can carry out 2 ~ 10 hours in the temperature range of 400 ~ 900 DEG C.When calcining temperature is less than 400 DEG C, is difficult to form iron lithium phosphate crystallization, when calcining temperature is greater than 900 DEG C, except iron lithium phosphate, also can forms by product.
On the other hand, above-mentioned calcining step can carry out under oxygen-free atmosphere or inert atmosphere.In one embodiment of this invention, above-mentioned calcining step can carry out under argon (Ar) gas atmosphere.
When making lithium iron phosphate nano powder by above-mentioned calcining, the glycols reaction solvent that a part residues in solids component is carbonized in calcination process, thus on the surface of the primary particle of lithium iron phosphate nano powder, form carbon overlay.
In detail, in calcining step, the part residuing in the glycols solvent on solids component is carbonized, thus overlay is formed on the surface of primary particle, all the other parts are while evaporation, while bring out aggregation between the primary particle of prepared above-mentioned lithium iron phosphate nano powder, thus prepare the lithium iron phosphate nano powder comprising the offspring with uniform particle size and distribution.Therefore, according to the present invention, when preparing the lithium iron phosphate nano powder of carbon coating, due to without the need to through being used for the extra process of coating carbon, thus the efficiency of operation and economy high.On the other hand, the carbon overlay be formed on the surface of particle has electroconductibility, thus has the effect of the conductance of the deficiency of supplementary lithium iron phosphate nano powder.
The lithium iron phosphate nano powder prepared by above-mentioned series of steps, primary particle has olivine crystal structure, and comprises the offspring condensed by plural above-mentioned primary particle.
Above-mentioned primary particle, as other unit cell forming offspring, has olivine crystal structure.Further, above-mentioned primary particle comprises the carbon overlay on part surface or the whole surface being coated on primary particle equably.
The thickness of above-mentioned carbon overlay can be 0.5 ~ 5nm, and above-mentioned carbon overlay is formed at the surface of particle, thus has the effect of the conductance of supplementary iron lithium phosphate compound.
On the other hand, the median size (D50) of above-mentioned primary particle can be 20 ~ 100nm, and the median size (D50) of the offspring condensed by multiple above-mentioned primary particle can be 50 ~ 1000nm.The size-grade distribution of the median size of the offspring prepared according to one embodiment of the invention can be even, and such as, above-mentioned size-grade distribution can be (with reference to figure 3) within 15%.
the embodiment of lithium secondary battery
Further, the present invention can providing package containing the positive active material of lithium iron phosphate nano powder of above-mentioned olivine crystal structure.Above-mentioned positive active material, except comprising iron phosphate powder, can also optionally comprise electro-conductive material, tackiness agent and weighting agent.
As long as above-mentioned electro-conductive material can not cause chemical transformation to battery and have electroconductibility, just not by particular restriction, such as, the graphite such as natural graphite or synthetic graphite can be used; The carbon black such as carbon black, acetylene black, Ketjen black, thermally oxidized black, furnace treated black, dim and thermal black; The conducting fibre such as carbon fiber or steel fiber; The metal-powders such as fluorocarbons, aluminium, nickel by powder; Zinc oxide, the electroconductibility whiskers such as potassium titanate; The conductive metal oxides such as titanium oxide; The conductive materials such as polyphenylene derivatives.
With the gross weight of the mixture containing positive active material for benchmark, the above-mentioned electro-conductive material of 1 to 30 weight percent usually can be comprised.
As long as the composition of the combination of above-mentioned tackiness agent auxiliary active agent and electro-conductive material etc. and the combination to current collector, just not by particular restriction, such as, can use polyvinylidene difluoride (PVDF), polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, polyacrylic acid, terpolymer EP rubber (EPDM), sulfonated EPDM, styrene-butadiene rubber(SBR), viton and multiple multipolymer etc.
With all wts of the mixture containing positive active material for benchmark, the above-mentioned tackiness agent of 1 to 30 weight percent usually can be comprised.
Above-mentioned weighting agent, as can optionally use as the composition for suppressing electrode expansion, as long as can not cause the fibrous material of chemical transformation to associated batteries, just not by particular restriction, such as, can use the olefin polymer such as polyethylene, polypropylene; The fibrous material such as glass fibre, carbon fiber.
Further, one embodiment of the invention provides above-mentioned positive active material to be coated on positive electrode for lithium secondary battery on current collector.
Above-mentioned positive electrode for lithium secondary battery by after such as above-mentioned positive active material being dissolved in solvent and making slurry, be coated on current collector, and the mode of carrying out drying and calendering can be made.
As long as above-mentioned positive electrode collector can not cause chemical transformation to associated batteries and have electroconductibility, just not by particular restriction.Such as, stainless steel, aluminium, nickel, titanium, calcining carbon can be used or utilizing carbon, nickel, titanium and silver etc. to carry out surface-treated material etc. to aluminium or stainless surface.
On the other hand, the thickness of above-mentioned current collector can be 3 to 500 μm usually, and current collector can form on its surface the cohesive force that micro concavo-convex improves positive active material.Such as can use with variforms such as film, thin slice, paper tinsel, net, porous insert, foam and non-woven body.
Further, one embodiment of the invention can provide the lithium secondary battery be made up of the positive pole comprising above-mentioned positive active material (cathode), negative pole (anode), barrier film and the nonaqueous electrolyte containing lithium salts.
Above-mentioned negative pole carries out drying to make after such as on negative electrode collector, coating comprises the negative pole mixture of negative electrode active material, and above-mentioned negative pole mixture can comprise the compositions such as electro-conductive material as above, tackiness agent and weighting agent as required.
As long as above-mentioned negative electrode collector can not cause chemical transformation to battery and have high conductivity, just not by particular restriction, such as, copper, stainless steel, aluminium, nickel, titanium, calcining carbon, copper can be used or utilize carbon, nickel, titanium and silver etc. to carry out surface-treated material, aluminium-cadmium alloy etc. to stainless surface.
On the other hand, the thickness of above-mentioned current collector usually can be 3 μm to 500 μm, the same with positive electrode collector, micro concavo-convex can be formed on the surface of above-mentioned current collector, strengthen the engaging force of negative electrode active material.Such as can use with variforms such as film, thin slice, paper tinsel, net, porous insert, foam and non-woven body.
Above-mentioned barrier film is located between positive pole and negative pole, can use the film of the insulativity with high iontophoretic injection degree and mechanical strength.
The hole diameter of barrier film can be 0.01 to 10 μm usually, thickness is generally 5 to 300 μm.
As above-mentioned barrier film, such as, can use there is the olefin polymer such as chemical resistant properties and hydrophobic polypropylene; The thin slice be made up of glass fibre or polyethylene etc. or non-woven fabrics.
At solid electrolytes such as use polymkeric substance as in electrolytical situation, solid electrolyte can double as barrier film.
The above-mentioned nonaqueous electrolyte containing lithium salts is made up of electrolytic solution and lithium salts, as above-mentioned electrolytic solution, uses non-water class organic solvent or organic solid electrolyte based.
Above-mentioned non-water class organic solvent can use such as METHYLPYRROLIDONE, propylene carbonate, NSC 11801, butylene, methylcarbonate, diethyl carbonate, gamma-butyrolactone, 1, 2-glycol dimethyl ether, tetrahydroxy furans, 2-methyltetrahydrofuran, dimethyl sulfoxide (DMSO), 1, 3-dioxolane, methane amide, dimethyl formamide, dioxolane, acetonitrile, Nitromethane 99Min., methyl-formiate, methyl acetate, phosphotriester, trimethoxy-methane, dioxolane derivatives, tetramethylene sulfone, methyl sulfolane, 1, 3-dimethyl-2-imidazolidinone, propylene carbonate ester derivative, tetrahydrofuran derivatives, ether, the non-proton organic solvent such as methyl propionate and ethyl propionate.
As above-mentioned organic solid electrolytic solution, such as polythene derivative, polyethylene oxide derivant, poly propylene oxide derivative, phosphate ester polymer, the poly-polymkeric substance stirring Methionin (poly agitation lysine), polyester sulfide, polyvinyl alcohol, polyvinylidene difluoride (PVDF) and contain the ionic base that dissociates can be used.
Above-mentioned lithium salts, as being easy to the material being dissolved in above-mentioned nonaqueous electrolytic, can use such as LiCl, LiBr, LiI, LiClO
4, LiBF
4, LiB
10cl
10, LiPF
6, LiCF
3sO
3, LiCF
3cO
2, LiAsF
6, LiSbF
6, LiAlCl
4, CH
3sO
3li, CF
3sO
3li, (CF
3sO
2)
2nLi, chlorine boron lithium, lower aliphatic carboxylic acid's lithium, 4-phenylo boric acid lithium and imide etc.
And, in order to improve charge-discharge characteristic, flame retardant resistance etc., such as pyridine, triethyl-phosphite, trolamine, cyclic ether, quadrol, n-glyme (glyme), six phosphoric triamides, nitrobenzene derivative, sulphur, quinonimine dye, N-substituted oxazolidine ketone, N, N-substituted imidazoline, glycol dialkyl ether, ammonium salt, pyrroles, 2-methyl cellosolve and aluminum chloride etc. can be added in the electrolytic solution.According to different situations, in order to give uninflammability, also can comprise the halogen-containing solvent such as tetracol phenixin, trifluoro-ethylene, and in order to improve High temperature storage characteristic, also can comprise carbon dioxide.
embodiment
Below, enumerate embodiment be described in detail to illustrate the present invention.But embodiments of the invention can change to variform, the present invention should not be construed as limit of the present invention in following embodiment.Embodiments of the invention provide to more intactly the present invention is described to general technical staff of the technical field of the invention.
embodiment 1
By the lithium hydroxide monohydrate (LiOHH of 6.29g
2o), the ironic citrate hydrate (FeC of 36.74g
6h
5o
7nH
2and the phosphoric acid (H of 14.7g O)
3pO
4) put into the ethylene glycol (ethylene glycol) of 500g, and utilize the mixing tank of high shear force (mixer, Chinese mugwort card (IKA) company) with the stirring of the rotating speed of 10000rpm through 30 minutes, to make it disperse equably.
In hot-plate, utilize bar magnet to stir with 400rpm rotating speed homodisperse above-mentioned mixing solutions, and the heating carried out at 200 DEG C of temperature 3 hours concentrates, thus prepare the glycollate slurry of 150g.
The glycollate slurry of above-mentioned gained is carried out to the drying of 10 hours at 120 DEG C of temperature, thus prepare ethylene glycol by the solids component evaporated.
Under argon (Ar) atmospheric condition, prepared above-mentioned solids component is carried out to the calcining of 5 hours in 500 DEG C of stoves (furnace), thus form the iron lithium phosphate individual particle (primary particle) (with reference to figure 1) of carbon coating, and prepared the lithium iron phosphate nano powder (with reference to figure 2) comprised by the iron lithium phosphate particle (offspring) of above-mentioned particle coacervation by successive reaction.
Further, the measurement result of the size-grade distribution of the lithium iron phosphate nano powder of above-mentioned preparation is presented in figure 3.
The physical property of primary particle and the offspring prepared in the manner is presented in lower list 1.
Embodiment 2
Prepare lithium iron phosphate nano powder in the same manner as in Example 1, but as iron precursor, drop into FeSO47H2O (FeSO
47H
2o) instead of ironic citrate hydrate.
The physical property of the offspring that prepared above-mentioned lithium iron phosphate nano powder comprises and the primary particle forming above-mentioned offspring is presented in lower list 1.
Embodiment 3
Prepare lithium iron phosphate nano powder in the same manner as in Example 1, but calcining temperature is set to 700 DEG C instead of 500 DEG C.
The physical property of the offspring that prepared above-mentioned lithium iron phosphate nano powder comprises and the primary particle forming above-mentioned offspring is presented in lower list 1.
Embodiment 4
Prepare lithium iron phosphate nano powder in the same manner as in Example 1, but drop into the ironic citrate hydrate of 35g.
The physical property of the offspring that prepared above-mentioned lithium iron phosphate nano powder comprises and the primary particle forming above-mentioned offspring is presented in lower list 1.
Embodiment 5
Prepare lithium iron phosphate nano powder in the same manner as in Example 1, but as solvent, use BDO (Isosorbide-5-Nitrae-butandiol) to instead of ethylene glycol.
The physical property of the offspring that prepared above-mentioned lithium iron phosphate nano powder comprises and the primary particle forming above-mentioned offspring is presented in lower list 1.
Comparative example 1
The physical property of the iron lithium phosphate compound particles utilizing existing common solid phase method to prepare is presented in lower list 1.
Table 1
Can confirm in table 1 above, the size of particles of lithium iron phosphate nano powder prepared according to the present invention and the thickness of carbon overlay obtain uniform control, can confirm in figure 3, according to the even particle size distribution of lithium iron phosphate nano powder prepared by the present invention.
experimental example 1 (preparation of lithium secondary battery)
step 1: the preparation utilizing the positive pole of iron lithium phosphate
Mix iron lithium phosphate, the carbon black as electro-conductive material and the polyvinylidene difluoride (PVDF) as tackiness agent (PVdF) prepared according to above-described embodiment and comparative example respectively using the weight percent of 95:3:2, and utilize N-Methyl pyrrolidone (NMP) solvent to make slurry.By the slurry coating made in aluminium foil, and at 130 DEG C of temperature, carry out the drying of 2 hours, thus implement roll-in after preparing positive pole.
step 2: the preparation of negative pole
As negative pole, using the weight percent mixing natural graphite of 93:1:6, the carbon black as electro-conductive material and the styrene-butadiene rubber(SBR) as tackiness agent (SBR), thus make slurry.By the slurry coating made in Copper Foil, and at 110 DEG C of temperature, carry out the drying of 2 hours, thus implement roll-in after preparing negative pole.
step 3: the assembling of battery
Utilize polyethylene diagrams (east combustion (Tonen) company, F20BHE, thickness=20 μm), and inject the electrolytic solution (lithium hexafluoro phosphate (LiPF of 1 mole
6), NSC 11801 (EC)/Methyl ethyl carbonate (EMC)=1/2 volume ratio) above-mentioned prepared positive pole and negative pole have finally been made Coin-shaped battery.
Charge and discharge electrical equipment is utilized to assess the characteristic of prepared battery under the voltage conditions of 3.0V to 4.3V.The result measured capacity and the energy density of prepared above-mentioned battery is as follows.
Table 2
Result with reference to above-mentioned table 2 can confirm, comprise the lithium secondary battery of the lithium iron phosphate nano powder made according to embodiments of the invention (embodiment 1 to embodiment 5), compared with the lithium secondary battery of the lithium iron phosphate nano powder constituent by comparative example 1, in cell container and energy density, present augmented performance result.
Claims (20)
1. a preparation method for carbon coating lithium iron phosphate nano powder, is characterized in that, comprising:
Step (a), puts into lithium precursor, iron precursor and phosphorus precursor to prepare mixing solutions in glycols solvent;
Step (b), drops into above-mentioned mixing solutions to reactor and carries out heating and concentrate and prepare oxyacetic acid metal paste;
Step (c), carries out drying to form solids component to above-mentioned oxyacetic acid metal paste; And
Step (d), carries out calcining to prepare carbon coating lithium iron phosphate nano powder to above-mentioned solids component.
2. the preparation method of carbon coating lithium iron phosphate nano powder according to claim 1, it is characterized in that, the heating of described step (b) is concentrated to be referred to, concentrates in the mode of carrying out heating at the temperature more than the boiling point of used described glycols solvent.
3. the preparation method of carbon coating lithium iron phosphate nano powder according to claim 1, it is characterized in that, the heating carrying out described step (b) under the pressure condition under 10 Palestine and Israels concentrates.
4. the preparation method of carbon coating lithium iron phosphate nano powder according to claim 1, is characterized in that, in the inside of convection oven, carry out the drying of described step (c) with the temperature range of 100 ~ 180 DEG C.
5. the preparation method of carbon coating lithium iron phosphate nano powder according to claim 1, it is characterized in that, the calcining of described step (d) carries out 2 ~ 10 hours in the temperature range of 400 ~ 900 DEG C.
6. the preparation method of carbon coating lithium iron phosphate nano powder according to claim 1, is characterized in that, under oxygen-free atmosphere or inert atmosphere, carry out described step (d).
7. the preparation method of carbon coating lithium iron phosphate nano powder according to claim 1, it is characterized in that, described glycols solvent is selected from the group be made up of ethylene glycol, Diethylene Glycol and BDO.
8. the preparation method of carbon coating lithium iron phosphate nano powder according to claim 1, it is characterized in that, described lithium precursor is be selected from one or more the mixture in the group that is made up of Lithium Acetate dihydrate, lithium hydroxide monohydrate, lithium hydroxide, Quilonum Retard, Trilithium phosphate, Trilithium phosphate dodecahydrate and lithium oxalate.
9. the preparation method of carbon coating lithium iron phosphate nano powder according to claim 1, it is characterized in that, described iron precursor is be selected from one or more the mixture in the group that is made up of ironic citrate, ironic citrate hydrate, FeSO47H2O, Ferrox dihydrate, ferric acetyl acetonade, tertiary iron phosphate dihydrate and ironic hydroxide.
10. the preparation method of carbon coating lithium iron phosphate nano powder according to claim 1, it is characterized in that, described phosphorus precursor is be selected from one or more the mixture in the group that is made up of ammonium phosphate trihydrate, Secondary ammonium phosphate, primary ammonium phosphate and phosphoric acid.
11. 1 kinds of carbon coating lithium iron phosphate nano powder, is characterized in that,
Carbon coating lithium iron phosphate nano powder packets prepared by the preparation method of carbon coating lithium iron phosphate nano powder according to claim 1 contains the offspring condensed by multiple primary particle, and described primary particle has olivine crystal structure;
Carbon overlay is formed on the part surface of described primary particle or whole surface.
12. carbon coating lithium iron phosphate nano powder according to claim 11, it is characterized in that, the thickness of described carbon overlay is 0.5 ~ 5nm.
13. carbon coating lithium iron phosphate nano powder according to claim 11, it is characterized in that, the median size (D50) of described primary particle is 20 ~ 100nm.
14. carbon coating lithium iron phosphate nano powder according to claim 11, it is characterized in that, the median size (D50) of described offspring is 50 ~ 1000nm.
15. carbon according to claim 11 coating lithium iron phosphate nano powder, is characterized in that, the size-grade distribution of the median size of described offspring is within 15%.
16. carbon coating lithium iron phosphate nano powder according to claim 11, it is characterized in that, described iron lithium phosphate is LiFePO
4.
17. 1 kinds of positive active materials, is characterized in that, comprise carbon according to claim 11 coating lithium iron phosphate nano powder.
18. positive active materials according to claim 17, is characterized in that, described positive active material also comprises and is selected from by more than one in electro-conductive material, tackiness agent and weighting agent.
19. 1 kinds of positive electrode for lithium secondary batterys, is characterized in that, comprise positive electrode collector and are coated on the positive active material according to claim 17 on described positive electrode collector.
20. 1 kinds of lithium secondary batteries, is characterized in that, comprise positive electrode for lithium secondary battery according to claim 19, negative pole, barrier film and the nonaqueous electrolytic solution containing lithium salts.
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| KR1020140002571A KR101580030B1 (en) | 2013-07-09 | 2014-01-08 | Method for manufacturing lithium iron phosphate nanopowder coated with carbon |
| PCT/KR2014/000266 WO2015005551A1 (en) | 2013-07-09 | 2014-01-09 | Method for preparing nanopowder of carbon-coated lithium metal phosphate |
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| WO2015005551A1 (en) | 2015-01-15 |
| US10153488B2 (en) | 2018-12-11 |
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| EP2883840A1 (en) | 2015-06-17 |
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